High efficiency catalyst containing titanium and zirconium for polymerizing olefins

ABSTRACT

Compositions exhibiting high catalytic activity in the polymerization of α-olefins, particularly higher olefins, are prepared by reacting trivalent or tetravalent titanium compounds such as titanium trichloride or titanium tetraalkoxide, zirconium compounds such as tri-n-butoxy zirconium chloride, an organomagnesium component such as di-n-hexyl magnesium, a halogen source such as ethyl aluminum dichloride and an organoaluminum compound if the halide source or magnesium component does not contain sufficient quantities of aluminum. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics and these catalysts produce polymers having broader molecular weight distributions and, at higher zirconium amounts, lower melt indices than do corresponding catalysts without the zirconium compound.

BACKGROUND OF THE INVENTION

This invention relates to a new catalyst composition useful for initiating and promoting polymerization of α-olefins and to a polymerization process employing such a catalyst composition.

It is well known that olefins such as ethylene, propylene and 1-butene in the presence of metallic catalysts, particularly the reaction products of organometallic compounds and transition metal compounds, can be polymerized to form substantially unbranched polymers of relatively high molecular weight. Typically such polymerizations are carried out at relatively low temperatures and pressures.

Among the methods for producing such linear olefin polymers, some of the most widely utilized are those described by Professor Karl Ziegler in U.S. Pat. Nos. 3,112,115 and 3,257,332. In these methods, the catalyst employed is obtained by admixing a compound of a transition metal of Groups IVB, VB, VIB and VIII of Mendeleev's Periodic Table of Elements with an organometallic compound. Generally, the halides, oxyhalides and alkoxides or esters of titanium, vanadium and zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydrides, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal borohydrides, alkali metal hydrides, alkaline earth metal hydrides and the like. Usually, polymerization is carried out in a reaction medium comprising an inert organic liquid, e.g., an aliphatic hydrocarbon and the aforementioned catalyst. One or more olefins may be brought into contact with the reaction medium in any suitable manner. A molecular weight regulator, which is normally hydrogen, is usually present in the reaction vessel in order to suppress the formation of undesirably high molecular weight polymers.

Following polymerization, it is common to remove catalyst residues from the polymer by repeatedly treating the polymer with alcohol or other deactivating agents such as aqueous base. Such catalyst deactivation and/or removal procedures are expensive both in time and material consumed as well as the equipment required to carry out such treatment.

Furthermore, most of the aforementioned known catalyst systems are more efficient in preparing polyolefins in slurry (i.e., wherein the polymer is not dissolved in the carrier) than in solution (i.e., wherein the temperature is high enough to solubilize the polymer in the carrier). The lower efficiencies of such catalysts in solution polymerization is believed to be caused by the general tendency of such catalysts to become rapidly depleted or deactivated by the significantly higher temperatures that are normally employed in solution processes. In addition, processes involving the copolymerization of ethylene with higher α-olefins exhibit catalyst efficiencies significantly lower than ethylene homopolymerization processes.

Recently, catalysts having higher efficiencies have been disclosed, e.g., U.S. Pat. No. 3,392,159, U.S. Pat. No. 3,737,393, West German Patent Application No. 2,231,982 and British Pat. Nos. 1,305,610, and 1,358,437. While the increased efficiencies achieved by using these recent catalysts are significant, even higher efficiencies are desirable, particularly in copolymerization processes. These high efficiency catalysts generally produce polymers of relatively narrow molecular weight distribution. It is therefore desirable to have, for some applications such as for use in injection molding, high efficiency catalysts which produce polymers and copolymers having a broader molecular weight distribution.

In view of the foregoing problems encountered in the use of conventional Ziegler catalysts, it would be highly desirable to provide a polymerization catalyst that is sufficiently active, even at solution polymerization temperatures above 140° C., to produce such high quantities of olefin homopolymers or copolymers per unit of catalyst that it is no longer necessary to remove catalyst residue in order to obtain a polymer of the desired purity.

SUMMARY OF THE INVENTION

The present invention, in one aspect, is the catalytic reaction product of (A) a trivalent or tetravalent titanium compound or mixture of such compounds, (B) a zirconium compound or mixture of such compounds, (C) an organomagnesium component and (D) a halide source. If components (C) and/or (D) do not contain sufficient quantities of an aluminum compound, then additional quantities of an organoaluminum compound should be added. The magnesium component is (1) a complex of an organomagnesium compound and an organometallic compound which solubilizes the organomagnesium compound or (2) a hydrocarbon soluble organomagnesium compound. The halide source is a non-metallic halide corresponding to the empirical formula R'X where in R' is hydrogen or an active monovalent organic radical and X is halogen. Alternatively, the halide source is a metallic halide corresponding to the empirical formula MR_(y-a) X_(a) wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of the Elements, R is a monovalent organic radical, usually hydrocarbyl or hydrocarbyloxy, X is halogen, y is a number corresponding to valence of M and a is a number from 1 to y. The proportions of the foregoing components of said catalytic reaction products are such that the atomic ratios of the elements are:

Mg:Zr is from about 1:1 to about 100:1; preferably from about 2.5:1 to about 50:1; most preferably from about 5:1 to about 25:1;

Al:Zr is from about 0.1:1 to about 100:1; preferably from about 0.5:1 to about 50:1; most preferably from about 1:1 to about 25:1;

Zr:Ti is from about 0.1:1 to about 50:1; preferably from about 0.5:1 to about 40:1; most preferably from about 1:1 to about 20:1;

excess X:Al is from about 0.0005:1 to about 10:1; preferably from about 0.002:1 to about 2:1; most preferably from about 0.01:1 to about 1.4:1.

The excess X is excess halide above that which would be theoretically required to convert the magnesium compound to the dihalide.

In a second aspect, the invention is a process for polymerizing at least one α-olefin under conditions characteristic of Ziegler polymerization wherein the aforementioned reaction product is employed as the sole catalyst when such contains aluminum or when there is additionally employed an organometallic compound containing aluminum if the catalyst does not contain aluminum.

In view of the reduced activity of conventional Ziegler catalysts in the copolymerization of α-olefins, particularly at solution polymerization temperatures, it is indeed surprising that the aforementioned catalytic reaction product is a high efficiency catalyst capable of producing more than a million pounds of olefin polymer or copolymer per pound of transition metal under such polymerization conditions. Accordingly, olefin polymers produced in accordance with the foregoing process generally contain lower amounts of catalyst residues than polymers produced in the presence of conventional catalyst even after subjecting such conventionally produced polymers to catalyst removal treatments. Further, these catalytic reaction products provide polymers produced therefrom with a relatively broader molecular weight distribution and, at higher zirconium amounts, a lower melt index than do corresponding catalysts without the zirconium compounds.

The catalyst formulations of the present invention are usually a dilute dark brown slurry of very fine particles. The MgCl₂ present is a fine, whitish precipitate with a surface area of about 250 m² /gm. The ZrCl₄ exhibits a wide range of particle size. If an alcohol is present, the solid ZrCl₄ dissolves, presumably to a compound of the general formula Zr(OR)_(x) Cl_(y), with O<x<4 and O<y<4. The extract structure of the Zr-Ti catalyst complex is not known.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is most advantageously practiced in a polymerization process wherein an α-olefin is polymerized, generally in the presence of hydrogen as a molecular weight control agent, in a polymerization zone containing an inert diluent and the catalytic reaction product as hereinbefore described. Especially advantageous is the copolymerization of ethylene and higher α-olefins using the catalytic reaction product of this invention. The foregoing polymerization process is most beneficially carried out under inert atmosphere and relatively low pressure, although very high pressures are optionally employed.

Olefins which are suitably homopolymerized or copolymerized in the practice of this invention are generally the aliphatic α-monoolefins or non-conjugated α-diolefins having from 2 to 18 carbon atoms. Illustratively, such α-olefins can include ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methylpentene-1, hexene-1, octene-1, dodecene-1, octadecene-1, 1,4-hexadiene, 1,7-octadiene and the like. It is understood that α-olefins may be copolymerized with other α-olefins and/or with small amounts, i.e., up to about 25 weight percent based on the polymer, of other ethylenically unsaturated monomers such as styrene, α-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts. Most benefits are realized in the polymerization of aliphatic α-monoolefins, particularly ethylene and mixtures of ethylene with up to 50, especially from about 0.1 to about 40, weight percent of propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, 1,4-hexadiene, 1,7-octadiene or similar α-olefin or non-conjugated α-diolefin based on total monomer.

As used herein, hydrocarbyl and hydrocarbyloxy are monovalent hydrocarbon radicals. Preferably, hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals having 1 to 20 carbon atoms, with alkyl having 1 to 10 carbon atoms being especially preferred. Likewise, preferably, hydrocarbyloxy is alkoxy, cycloalkyloxy, aryloxy, aralkyloxy, alkenyloxy and similar oxyhydrocarbon radicals having 1 to 20 carbon atoms, with alkyloxy with 1 to 10 carbon atoms being preferred.

Advantageously, the tetravalent titanium compound employed herein is represented by the empirical formula: TiX_(n) (OR)_(4-n), wherein X is a halogen, particularly chlorine or bromine, R is a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms, and n has a value of 0 to 4. Such titanium compounds are preferably derived from the titanium halides wherein one or more of the halogen atoms are replaced by an alkoxy or aryloxy group. Exemplary of such compounds include tetra-n-butoxy titanium, tetra(isopropoxy) titanium, di-n-butoxy titanium dichloride, monoethoxy titanium trichloride, tetraphenoxy titanium and the like.

Suitable trivalent compounds include α- and γ-TiCl₃ and the trivalent titanium complexes represented by the empirical formula: TiZ₃ (L)_(x) wherein Z is halide, and L is an electron donating compound such as water or an organic electron donor, e.g., alcohol, ether, ketone, amine, or olefin, and x is a whole number from 1 to 6. Usually, the organic electron donor has from 1 to 12 carbon atoms and donates an unshared pair of electrons to the complex. Exemplary electron donating compounds suitably employed include aliphatic alcohols, e.g., isopropyl alcohol, ethanol, n-propyl alcohol, butanol and others having from 1 to 12 carbon atoms; ethers; ketones; aldehydes; amines; olefins, and the like having from 1 to 20 carbon atoms; and water. In preferred complexes, z is chloride or bromide, most preferably chloride, and L is alcohol, especially an aliphatic alcohol having 2 to 8 carbon atoms and most preferably 3 to 6 carbon atoms, such as isopropyl alcohol, n-propyl alcohol, n-butyl alcohol and isobutyl alcohol. While the exact structure of the complex is not known, it is believed to contain 3 valence bonds to the halide ions and 1 to 6, preferably 2 to 4, coordination bonds to the electron donating compound. In addition to α-TiCl₃, the Δ, γ and β crystalline forms of titanium trichloride are advantageously employed in the preparation of the complex. Also suitable are titanium tribromide, titanium fluoride and the like. Of the foregoing, the γ- and α-forms of titanium trichloride are preferred. These complexes and their preparation are more fully described by Birkelbach in U.S. Pat. No. 4,120,820 which is incorporated herein by reference.

Suitable zirconium compounds which can be employed herein include those represented by the empirical formula: Zr(OR)_(x) X_(y), wherein each R is independently a hydrocarbyl group having from 1 to about 20, preferably 1 to about 10, carbon atoms, each X is independently a halogen atom, preferably chlorine or bromine, and x and y independently have values from zero to 4 with the value of x plus y being 4.

Particularly suitable zirconium compounds include, for example, ZrCl₄, ZrBr₄, Zr(OnBu)₄, Zr(OnPr)₄, Zr(OEt)₂ Cl₂, Zr(OEt)₂ Br₂, Zr(OnPr)₂ Cl₂, Zr(OnPr)₂ Br₂, Zr(OiPr)₂ Cl₂, Zr(OiPr)₂ Br₂, Zr(OnBu)₂ Cl₂, Zr(OnBu)₂ Br₂, mixtures thereof and the like. In the above formulae, Et=ethyl, iPr=isopropyl, nPr=normal propyl, and nBu=normal butyl.

The zirconium compounds represented by the empirical formula Zr(OR)_(x) X_(y) wherein 0≦x<4 can be prepared in situ by adding a zirconium tetrahalide and an aliphatic alcohol having from 1 to about 20, preferably 1 to about 10, carbon atoms to the catalytic reaction mixture as the zirconium component. The mole ratio of alcohol to zirconium halide is from about 0.01 to about 10, preferably from about 0.25 to about 4.

The preferred organomagnesium component is a hydrocarbon soluble complex illustrated by the empirical formula MgR"₂.xMR"_(y) wherein R" is independently hydrocarbyl or hydrocarbyloxy, M is aluminum, zinc, boron, silicon, tin, phosphorous or mixtures thereof, x is about zero to 10, especially from about zero to about 0.25, and y denotes the number of hydrocarbyl groups which corresponds to the valence of M. In order to obtain maximum catalyst efficiency at polymerization temperatures above 180° C., it is desirable to minimize the amount of aluminum in the complex as well as in the total catalyst. Accordingly, for catalysts having Al:Ti atomic ratios less than 120:1, it is desirable to have a Mg:Al atomic ratio more than 0.3:1, preferably from about 0.5:1 to 10:1.

Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium such as the magnesium dialkyls and the magnesium diaryls. Exemplary suitable magnesium dialkyls include particularly n-butyl-sec-butyl magnesium, diisopropyl magnesium, di-n-hexyl magnesium, isopropyl-n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesium and others wherein each alkyl has from 1 to 20 carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium and ditolylmagnesium. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides, and aryl and alkyl magnesium halides with the halogen-free organomagnesium compounds being more desirable.

Suitable hydrocarbon soluble organomagnesium compounds and/or complexes are commercially available from Texas Alkyls, Inc., Lithium Corporation of America and Schering AG Industrie-Chemikalien.

The preferred halide sources are the active non-metallic halides of the formula set forth hereinbefore including hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein hydrocarbyl is as defined hereinbefore. By an active organic halide is meant a hydrocarbyl halide that contains a labile halogen at least as active, i.e., as easily lost to another compound, as the halogen of sec-butyl chloride, preferably as active as t-butyl chloride. In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides that are active as defined hereinbefore are also suitably employed. Examples of preferred active non-metallic halides include hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, methylvinyl carbinyl chloride, α-phenylethyl bromide, and diphenyl methyl chloride.

Suitable metallic halides as set forth by formula hereinbefore are organometallic halides and metal halides wherein the metal is in Group IIIA or IVA of Mendeleev's Periodic Table of Elements. Preferred metallic halides are aluminum halides of the empirical formula AlR_(3-a) X_(a) wherein each R is independently hydrocarbyl as hereinbefore defined such as alkyl, X is a halogen and a is a number from 1 to 3. Most preferred are alkylaluminum halides such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with ethylaluminum dichloride being especially preferred. Alternatively, a metal halide such as aluminum trichloride or a combination of aluminum trichloride with an alkyl aluminum halide or a trialkyl aluminum compound may be suitably employed.

It is understood that the organic moieties of the aforementioned organomagnesium, e.g., R", and the organic moieties of the halide source, e.g., R and R', are suitably any other organic radical provided that they do not contain functional groups that poison conventional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e., those sufficiently active to react with the Zerewitinoff reagent.

For ease of catalyst preparation the catalyst is prepared by mixing the components of the catalyst in an inert liquid diluent in the following order: (a) the halide source, (b) if required, the aluminum compound, (c) the titanium compound, (d) the zirconium compound and (e) the organomagnesium component. It is understood, however, that any suitable order of addition can be employed as long as the titanium and/or zirconium compound is not over-reduced by the other catalyst components (over-reduction is evidenced by a drastic drop in catalyst efficiency or total inactivity of the catalyst).

The foregoing catalyst components are combined in proportions sufficient to provide atomic ratios as previously mentioned.

In cases wherein neither the organomagnesium component nor the halide source contains aluminum, it is necessary to include in the total catalyst an aluminum compound such as an alkyl aluminum compound, e.g., a trialkyl aluminum, an alkyl aluminum halide or an aluminum halide. If polymerization temperatures below 180° C. are employed, the atomic ratios of Al:Ti may be from about 0.1:1 to about 2000:1, preferably from 1:1 to 200:1. However, when polymerization temperatures above 180° C. are employed, the aluminum compound is used in proportions such that the Mg:Al ratio is more than 0.3:1, preferably from 0.5:1 to 10:1, and Al:Ti ratio is less than 120:1, preferably less than 50:1. It is understood, however, that the use of very low amounts of aluminum necessitates the use of high purity solvents or diluents in the polymerization zone. Further, other components present in the zone should be essentially free of impurities which react with aluminum alkyls. Otherwise, additional quantities of an organometallic compound as previously described, preferably an organoaluminum compound, must be used to react with such impurities. Moreover, it is understood that in the catalyst the aluminum compound should be in the form of trialkyl aluminum or alkyl aluminum halide provided that the alkyl aluminum halide be substantially free of alkyl aluminum dihalide.

The foregoing catalytic reaction is preferably carried out in the presence of an inert diluent. The concentrations of catalyst components are preferably such that when the essential components of the catalytic reaction product are combined, the resultant slurry is from about 0.0005 to about 1.0 molar (moles/liter) with respect to magnesium. By way of an example of suitable inert organic diluents can be mentioned liquefied ethane, propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene, naphthas, etc., especially when freed of any olefin compounds and other impurities, and especially those having boiling points in the range from about -50° to about 200° C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene, cumene, decalin and the like.

Mixing of the catalyst components to provide the desired catalytic reaction product is advantageously carried out under an inert atmosphere such as nitrogen. argon or other inert gas at temperatures in the range from about -100° to about 200° C., preferably from about 0° to about 100° C. The period of mixing is not considered to be critical as it is found that a sufficient catalyst composition most often occurs within about 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to separate hydrocarbon soluble components from hydrocarbon insoluble components of the reaction product.

In the polymerization process employing the aforementioned catalytic reaction product, polymerization is effected by adding a catalytic amount of the above catalyst composition to a polymerization zone containing α-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from about 0° to about 300° C., preferably at solution polymerization temperatures, e.g., from about 130° to about 250° C., for a residence time of about a few seconds to several days, preferably 15 seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen with a catalytic amount of the catalytic reaction product being within the range from about 0.0001 to about 0.1 millimoles titanium per liter of diluent. It is understood, however, that the most advantageous catalyst concentration will depend upon polymerization conditions such as temperature, pressure, solvent and presence of catalyst poisons, and that the foregoing range is given to obtain maximum catalyst yields in weight of polymer per unit weight of titanium.

Generally in the polymerization process, a carrier is employed which may be an inert organic diluent or solvent of excess monomer. In order to realize the full benefit of the high efficiency catalyst of the present invention, care must be taken to avoid oversaturation of the solvent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalyst is not realized. For best results, it is preferred that the amount of polymer in the carrier not exceed about 50 weight percent based on the total weight of the reaction mixture.

It is understood that inert diluents employed in the polymerization recipe are suitably as defined hereinbefore.

The polymerization pressures preferably employed are relatively low, e.g., from about 50 to about 1000 psig, especially from about 100 to about 700 psig. However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the capabilities of the polymerization equipment. During polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone.

In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to maintain an ethylene concentration in the solvent in the range of from about 1 to about 10 weight percent, most advantageously from about 1.2 to about 2 weight percent. To achieve this, when an excess of ethylene is fed into the system, a portion of the ethylene can be vented.

Hydrogen can be employed in the practice of this invention to lower the molecular weight of the resultant polymer. For the purpose of this invention, it is beneficial to employ hydrogen in concentrations ranging from about 0.001 to about 1 mole per mole of monomer. The larger amounts of hydrogen within this range are found to produce generally lower molecular weight polymers. It is understood that hydrogen can be added with a monomer stream to the polymerization vessel or separately added to the vessel before, during or after addition of the monomer to the polymerization vessel, but during or before the addition of the catalyst.

The monomer or mixture of monomers is contacted with the catalytic reaction product in any conventional manner, preferably by bringing the catalytic reaction product and monomer together with intimate agitation provided by suitable stirring or other means. Agitation can be continued during polymerization, or in some instances, the polymerization mixture can be allowed to remain unstirred while the polymerization takes place. In the case of more rapid reactions with more active catalysts, means can be provided for refluxing monomer(s) and solvent, if any of the latter is present, thus removing the heat of reaction. In any event, adequate means should be provided for dissipating the exothermic heat of polymerization. If desired, the monomer(s) can be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization can be effected in the batch manner, or in a continuous manner, such as, for example, by passing the reaction mixture through an elongated reaction tube which is contacted externally with suitable cooling medium to maintain the desired reaction temperature, or by passing the reaction mixture through an equilibrium overflow reactor or a series of the same.

The polymer is readily recovered from the polymerization mixture by driving off unreacted monomer or solvent if employed. No further removal of impurities is required. Thus, a significant advantage of the present invention is the elimination of the catalyst residue removal steps. In some instances, however, it may be desirable to add a small amount of a catalyst deactivating reagent of the types conventionally employed for deactivating Ziegler catalysts. The resultant polymer is found to contain insignificant amounts of catalyst residue and to possess a relatively broad molecular weight distribution.

The following examples are given to illustrate the invention, and should not be construed as limiting its scope. All parts are by molar ratio and percentages are by weight unless otherwise indicated.

In the following examples, the melt index values I₂ and I₁₀ were determined by ASTM D 1238-70 and the density values were determined by ASTM D 1248.

The following abbreviations are employed in the examples.

BEM=n-butyl ethyl magnesium

nBu=normal butyl

DBM=n-butyl-sec-butyl magnesium

DNHM=di-n-hexyl magnesium

EADC=ethyl aluminum dichloride

Et=ethyl

M=molar

Me=methyl

iPr=isopropyl

nPr=normal propyl

EXAMPLES 1-3 A. Preparation of Zr(OnBu)₃ Cl

To 4.22 gms (0.011 moles) of neat Zr(OnBu)₄ was added sufficient Isopar® E (an isoparaffinic hydrocarbon fraction boiling in the range of 116°-134° C.) to bring the total volume to 100.0 ml. Anhydrous electronic grade HCl was passed through the solution until a milky precipitate was formed. Excess HCl was stripped from the mixture by passing dry N₂ through the solution.

B. Preparation of the Catalyst Composition

The catalysts used were prepared by mixing in an inert atmosphere the following components in the order indicated:

    ______________________________________                                         96.97 - x ml                                                                              of Isopar® E                                                    1.05 ml    of 0.95 EADC                                                        x ml       of 0.011 M Zr(OnBu).sub.3 Cl                                        0.6  ml    of 0.0336 M Ti(OiPr).sub.4                                          1.38 ml    of 0.58 M DNHM (as obtained commer-                                 100.0  ml  cially from Texas Alkyls, Inc. as                                              MAGALA® DNHM)                                                   ______________________________________                                    

where x can be determined from the following table:

    ______________________________________                                         Example        x, ml  Zr:Ti Ratio                                              ______________________________________                                         1              0.23   1/8:1                                                    2              0.45   1/4:1                                                    3              0.91   1/2:1                                                    ______________________________________                                    

C. Polymerization

A stirred batch reactor containing 2 liters of Isopar® E was heated to 150° C. The solvent vapor pressure was 21 psig. To this was added 19 psig of hydrogen and 120 psig of ethylene for a total reactor pressure of 160 psig. An amount of the above catalyst (wherein 7.5 ml=0.0015 mMoles Ti) was injected into the reactor, and the reactor pressure was maintained constant at 160 psig with ethylene. The total reaction time was 30 minutes. The catalyst efficiency can be found in Table I with polymer physical properties found in Table II.

EXAMPLES 4-6 AND COMPARATIVE EXPERIMENT A A. Preparation of the Catalyst Composition

The catalysts used were prepared under conditions similar to those for the catalyst preparation in examples 1-3. The following components were mixed in the following order:

    ______________________________________                                         97.57 - x ml                                                                              of Isopar® E                                                    1.05 ml    of 0.95M EADC                                                       x ml       of the Ti(OiPr).sub.4 --Zr(OnBu).sub.3 Cl mixture                   1.38 ml    of 0.58 M DNHM (as obtained commer-                                 100.0  ml  cially from Texas Alkyls, Inc. as                                              MAGALA® DNHM)                                                   ______________________________________                                    

where x can be determined from the following table:

    ______________________________________                                                          Concen-    Concen-                                                             tration    tration                                            Example   x, ml  Ti         Zr     Zr:Ti Ratio                                 ______________________________________                                         4         0.8    0.025      0.100  4:1                                         5         1.54   0.013      0.100  8:1                                         6         3.33   0.006      0.100  16:1                                         A*       0.6    0.0336     0.0    0:1                                         ______________________________________                                          *comparative                                                             

B. Polymerization

Polymerization conditions were identical to those for examples 1-3. Catalyst efficiency can be found in Table I and polymer properties are listed in Table II.

COMPARATIVE EXPERIMENT B A. Preparation of the Catalyst Composition

The catalyst for this run was prepared under similar conditions as for examples 1-3. The following components were mixed in the following order:

    ______________________________________                                         97.60 ml     of Isopar® E                                                  0.79 ml      of 0.95 EADC                                                      0.14 ml      of Zr(OnBu).sub.3 Cl                                              1.46 ml      of 0.405 M DBM (as obtained                                       100.0  ml    commercially from Lithium                                                      Corporation of America)                                           ______________________________________                                    

B. Polymerization

Polymerization conditions were identical to those for examples 1-3. Addition of 0.0075 mMoles of Zr (50 ml of catalyst) produced no observable polymer.

COMPARATIVE EXPERIMENT C A. Preparation of Catalyst and Polymerization

A comparative catalyst similar to that described in Comparative Experiment A was prepared and polymerization was carried out as outlined in examples 1-3.

EXAMPLES 7-8 A. Preparation of Zr(OnBu)₃ Cl

To 50.0 ml of Isopar® E is added 1.17 gm of ZrCl₄. Then, with rapid stirring, 1.37 ml of neat nBuOH is added. This produces a solution containing 0.1 M Zr.

B. Preparation of the Catalyst Composition

The catalysts used in these runs were prepared under similar conditions as for examples 1-3. The following components were mixed in the following order:

    ______________________________________                                         97.68 - x ml                                                                               of Isopar® E                                                   0.75 ml     of 1.00 M EADC                                                     0.60 ml     of 0.025 M Ti(OiPr).sub.4                                          x ml        of 0.1 M Zr(OnBu).sub.3 Cl (as prepared                                        in A above)                                                        0.97 ml     of 0.62 M BEM (as obtained commer-                                 100.0  ml   cially from Texas Alkyls, Inc.                                                 as MAGALA® BEM)                                                ______________________________________                                    

where x can be determined from the following table:

    ______________________________________                                         Example        x, ml  Zr:Ti Ratio                                              ______________________________________                                         7              2.4    16:1                                                     8              1.2     8:1                                                     ______________________________________                                    

C. Polymerization

Polymerization conditions were identical to those for examples 1-3. Catalyst efficiency can be found in Table I and polymer properties are listed in Table II.

EXAMPLE 9 AND COMPARATIVE EXPERIMENT D A. Preparation of the Catalyst Composition

The catalysts used were prepared under conditions similar to those for the catalyst preparation in examples 1-3. The following components were mixed in the following order:

    ______________________________________                                         97.68 - x - y ml                                                                            of Isopar® E                                                  0.75 ml      of 1.00 EADC                                                      0.6  ml      of 0.025 M Ti(OiPr).sub.4                                         x ml         of 0.1 M ZrCl.sub.4 (slurry in Isopar® E)                     y ml         of 0.3 M n-butanol                                                0.97 ml      of 0.62 M BEM (as obtained commer-                                100.0   ml   cially from Texas Alkyls, Inc. as                                              MAGALA® BEM)                                                  ______________________________________                                    

where x and y can be determined from the following table:

    ______________________________________                                                                    Zr:Ti nBuOH:Zr                                      Example    x, ml  y, ml    Ratio Ratio                                         ______________________________________                                         9          1.2    1.2      8:1   3:1                                           D          1.2    0        8:1   --                                            ______________________________________                                    

B. Polymerization

Polymerization conditions were identical to those for examples 1-3. Catalyst efficiencies can be found in Table I and polymer properties are listed in Table II.

As can be seen in Table II in Examples 1 through 6 and Comparative Experiment A, increasing the level of the zirconium compound in the catalyst while holding all other factors constant leads to a lowering of the melt index from 16.4 gm/10 min. for a catalyst with no zirconium to 4.3 gm/10 min. for a catalyst containing 16 zirconiums. This is unexpected and provides a method of controlling the polymer's molecular weight (melt index) without adjusting the amount of the normal chain terminator (H₂).

Examples 7 and 8 again show this unexpected property of melt index lowering when compared to Comparative Experiment C. Example 9 and Comparative Experiment D also show melt index lowering because of the zirconium compound present, but Example 9 has a narrower molecular weight distribution, as evidenced by the I₁₀ /I₂ ratio, because of the presence of n-butyl alcohol in the mixture.

                                      TABLE I                                      __________________________________________________________________________                                Catalyst                                            Example &                  Atomic                                              Comparative                Ratios  Efficiency × 10.sup.-6.spsp.3         Experiment #                                                                          Catalyst Components Al/Ti/Zr/Mg                                                                            wt PE.sup.1 /wt Ti                                                                     wt PE/wt Ti + Zr                    __________________________________________________________________________     1      EADC/Ti(OiPr).sub.4 /Zr(OnBu).sub.3 Cl/BEM                                                         50/1/1/8/40                                                                            1.70    1.37                                2         "                50/1/1/4/40                                                                            1.88    1.27                                3         "                50/1/1/2/40                                                                            1.75    0.896                               4         "                50/1/4/40                                                                              1.35    0.157                               5         "                50/1/8/40                                                                              1.06    0.0653                              6         "                50/1/16/40                                                                             0.31    0.00985                             A      EADC/Ti(OiPr).sub.4 /BEM                                                                           50/1/0/40                                                                              1.75    1.75                                B      EADC/Zr(OnBu).sub.3 Cl/DBM                                                                         50/0/1/40                                                                              0.0     0.0                                 C      EADC/Ti(OiPr).sub.4 /DNHM                                                                          50/1/0/40                                                                              1.1     1.1                                 7      EADC/Ti(OiPr).sub.4 /Zr(OnBu).sub.3 Cl/BEM                                                         50/1/16/40                                                                             0.72    0.0229                              8         "                50/1/8/40                                                                              1.08    0.0665                              9      EADC/Ti(OiPr).sub.4 /ZrCl.sub.4 /nBuOH/BEM                                                         50/1/8/24.sup.2 /40                                                                    0.43    0.0265                              D      EADC/Ti(OiPr).sub.4 /ZrCl.sub.4 /BEM                                                               50/1/8/40                                                                              0.73    0.0450                              __________________________________________________________________________      .sup.1 PE is polyethylene.                                                     .sup.2 Mole ratio of moles of nbutyl alcohol to moles of Ti in the             catalyst.                                                                      .sup.3 Value indicated should be multiplied by 1 × 10.sup.6.       

                  TABLE II                                                         ______________________________________                                         Example &                                                                      Comparative                       DENSITY                                      Experiment #                                                                               I.sub.2                                                                               I.sub.10 I.sub.10 /I.sub.2                                                                    g/cc                                         ______________________________________                                         1           16.39  124.40   7.59  0.9678                                       2           17.31  127.22   7.35  0.9678                                       3           15.09  115.04   7.62  0.9671                                       4           8.93   68.51    7.67  0.9658                                       5           5.38   44.71    8.31  0.9651                                       6           4.30   36.08    8.39  0.9631                                       A           16.37  114.75   7.01  0.9663                                        B*         --     --       --    --                                           C           13.62  97.11    7.13  0.9673                                       7           1.84   19.96    10.85 0.9624                                       8           6.02   47.36    7.87  0.9649                                       9           2.48   22.16    8.94  0.9636                                       D           2.10   20.61    9.81  0.9619                                       ______________________________________                                          *no polymer produced                                                      

We claim:
 1. A catalytic reaction product of(A) a trivalent or tetravalent titanium compound represented by the empirical formulas (i) TiX_(n) (OR)_(4-n) wherein X is a halogen, R is a hydrocarbyl group having from 1 to about 20 carbon atoms and n has a value of zero to 4; (ii) α- and/or γ-TiCl₃ ; and (iii) TiZ₃ (L)_(x) wherein Z is a halogen and L is an electron donating compound selected from water, ketones, ethers, amines or olefins and x is a whole number from 1 to 6; (B) a zirconium compound represented by the empirical formula Zr(OR)_(x) X_(y) wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is independently a halogen atom and each x and y independently have values from zero to 4 with the value of x plus y being 4; (C) an organomagnesium component selected from(1) an organomagnesium compound or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium compound in a hydrocarbon solvent; said organomagnesium component being represented by the empircal formula MgR"₂.xMR"_(y) wherein M is aluminum, zinc, boron, silicon, tin or phosphorus; each R" is independently hydrocarbyl or hydrocarbyloxy having from 1 to about 20 carbon atoms; x has a value from zero to about 10 and y has a value corresponding to the valence of M; (D) a halide source selected from(1) an active non-metalic halide, said non-metallic halide corresponding to the empirical formula R'X wherein R' is hydrogen or an organic group at least as active as sec-butyl and X is halogen; or (2) a metallic halide corresponding to the empirical formula MR_(y-a) X_(a) wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of the Elements, R is a hydrocarbyl or hydrocarbyloxy group, X is halogen, y is a number corresponding to valence of M and a is a number from 1 to y; provided that the proportions of the foregoing components of said catalytic reaction product are such that the atomic ratio of Mg:Zr is from about 1:1 to about 100:1; the atomic ratio of Al:Zr is from about 0.1:1 to about 100:1; the atomic ratio of Zr:Ti is from about 0.5:1 to about 50:1; the atomic ratio of excess X:Al is from about 0.0005:1 to about 10:1; andfurther provided that when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, there is also present (E) an aluminum compound represented by the empirical formula AlR_(y') X_(y") wherein R and X are as defined above and y' and y" each have a value of from zero to three with the total value of y' plus y" being three;and wherein the components are added in an order selected from the group consisting of: (a) (i) component (C), (ii) component (D), (iii) component (E), if employed, followed by (iv) components (A) and (B) in any order or as a mixture; (b) (i) component (D) if it contains aluminum, (ii) component (C), (iii) components (A) and (B) in any order or as a mixture; and (c) (i) component (D) if aluminum is present, (ii) components (A) and (B) in any order or as a mixture and (iii) component (C).
 2. The catalytic product of claim 1 wherein the titanium compound is a tetravalent titanium compound represented by the empirical formula TiX_(n) (OR)_(4-n) and the zirconium compound is represented by the empirical formula Zr(OR)_(x) X_(y), wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each X is a halogen, x and y independently have values of from zero to 4 while the sum of x and y has a value of 4, n has a value of from zero to 4 and wherein the atomic ratio of Mg:Zr is from about 2.5:1 to about 50:1; the atomic ratio of Al:Zr is from about 0.5:1 to about 50:1; the atomic ratio of Zr:Ti is from about 0.5:1 to about 40:1; the atomic ratio of excess X:Al is from about 0.002:1 to about 2:1.
 3. The catalytic product of claim 2 wherein each X is halogen, each R independently has from 1 to about 10 carbon atoms, the atomic ratio of Mg:Zr is from about 5:1 to about 25:1; the atomic ratio of Al:Zr is from about 1:1 to about 25:1; the atomic ratio of Zr:Ti is from about 1:1 to about 20:1; the atomic ratio of excess X:Al is from about 0.01:1 to about 1.4:1.
 4. The catalytic product of claim 3 wherein the organomagnesium compound is a hydrocarbon soluble dihydrocarbyl magnesium.
 5. The catalytic product of claim 3 wherein the organomagnesium component is a complex of dialkyl magnesium and a trialkyl aluminum wherein the atomic ratio of Mg to Al in the organomagnesium component is within the range from about 0.5:1 to about 10:1.
 6. The catalytic product of claim 4 wherein the tetravalent titanium compound is tetraiospropoxy titanium, tetraethoxy titanium, tetra-n-butoxy titanium or tetramethoxy titanium.
 7. The catalytic product of claim 5 wherein the tetravalent titanium compound is tetraisopropoxy titanium, tetraethoxy titanium, tetra-n-butoxy titanium or tetramethoxy titanium.
 8. The catalytic product of claims 6 or 7 wherein the zirconium compound is Zr(OnBu)₃ Cl, Zr(OnBu)₄ or the product resulting from the combination of ZrX₄, wherein X is chlorine or bromine, and an aliphatic alcohol having from 1 to 8 carbon atoms in a mole ratio of zirconium halide to alcohol of from about 0.25:1 to about 4:1.
 9. The catalytic product of claims 1, 2, 3, 4, 5, 6 or 7 wherein the catalyst is prepared employing the order of addition designated as (a).
 10. The catalytic product of claims 1, 2, 3, 4, 5, 6 or 7 wherein the catalyst is prepared employing the order of addition designated as (b).
 11. The catalytic product of claims 1, 2, 3, 4, 5, 6 or 7 wherein the catalyst is prepared employing the order of addition designated as (c).
 12. The catalytic product of claim 8 wherein the catalyst is prepared employing the order of addition designated as (a).
 13. The catalytic product of claim 8 wherein the catalyst is prepared employing the order of addition designated as (b).
 14. The catalytic product of claim 8 wherein the catalyst is prepared employing the order of addition designated as (c). 